CN101760712A - Production method for hot dip galvanized steel sheet in high manganese steel with great coating surface quality - Google Patents
Production method for hot dip galvanized steel sheet in high manganese steel with great coating surface quality Download PDFInfo
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- CN101760712A CN101760712A CN200910254378A CN200910254378A CN101760712A CN 101760712 A CN101760712 A CN 101760712A CN 200910254378 A CN200910254378 A CN 200910254378A CN 200910254378 A CN200910254378 A CN 200910254378A CN 101760712 A CN101760712 A CN 101760712A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 27
- 238000000576 coating method Methods 0.000 title claims abstract description 27
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 20
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 229910000617 Mangalloy Inorganic materials 0.000 title abstract description 7
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 57
- 239000010959 steel Substances 0.000 claims abstract description 57
- 239000011572 manganese Substances 0.000 claims abstract description 43
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000007747 plating Methods 0.000 claims description 54
- 239000012298 atmosphere Substances 0.000 claims description 33
- 230000003647 oxidation Effects 0.000 claims description 33
- 238000007254 oxidation reaction Methods 0.000 claims description 33
- 239000011159 matrix material Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000005246 galvanizing Methods 0.000 claims description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 11
- 230000002829 reductive effect Effects 0.000 abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 238000003618 dip coating Methods 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 34
- 238000000137 annealing Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910000794 TRIP steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000010410 layer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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- Coating With Molten Metal (AREA)
Abstract
The invention relates to a production method for hot dip galvanized steel sheet in high ductility and high strength used in vehicular body and structural material, the object is to provide a method of easily producing high manganese steel with great coating surface qualities such as hot-dip coating property, coating adherence or the like using high manganese steel as the coating material. The invention provides a method for producing high manganese hot dip zinc coating steel plates in great coating surface quality using high manganese steel as the base, and is characterized in that the high manganese steel is optionally oxidized in a manner of regulating the dew point, the heating temperature and the heating time of the ambient gas, forming internal oxide and porous surface oxide closely below the base, reduced in the reduction ambient gas, then subject to hot dip zinc coating. According to the invention, high manganese hot dip zinc coating steel plate with great coating surface quality such as hot dip coating property, coating adherence or the like can be easily produced.
Description
Technical field
The present invention relates to the manufacture method of galvanizing high manganese steel sheet used in the vehicle body of automobile and structured material etc. with high ductibility and high-strength characteristic, more particularly, the present invention relates to the manufacture method of the high mangaenese steel hot-dip galvanized steel sheet of great coating surface qualities such as hot dipping plating and plating tackiness.
Background technology
Hot-dip galvanized steel sheet is widely used as automotive sheet owing to have superior corrosion resistance, weldability and coating.
On the other hand, because the lighting of automobile from improving the angle of fuel efficiency and security, is constantly sought the high strength of body of a motor car and structured material, thereupon, developed multiple automobile high-strength steel.
But most of steel plate reduces owing to high strength makes ductility, and the result causes that a lot of restrictions are arranged when being processed into parts.
The ductility that causes for the high strength that solves such steel plate reduces, many researchs have been carried out, the result has proposed austenite (austenite) class high mangaenese steel, this class steel contains 7～35% manganese in steel, when viscous deformation takes place, in steel, induce twin crystal (TWIN) to occur, thereby improved ductility (patent documentation 1, patent documentation 2, patent documentation 3, patent documentation 4 etc.) epoch-makingly.
But, using such high mangaenese steel as plating in the raw-material hot-dip galvanized steel sheet, in order to ensure material and make surface active (reduction), in hydrogenous nitrogen atmosphere atmosphere gas, anneal.
Such atmosphere gas is reductibility atmosphere gas for plating starting material Fe, but for the element of oxidation easily such as Mn, the Si of high mangaenese steel, Al, is to work as oxidisability atmosphere gas.Therefore, in such atmosphere gas, when the high mangaenese steel that is added with a large amount of Mn was carried out full annealed, micro-moisture that contains in the atmosphere gas and oxygen can make these alloying elements by selectivity oxidation (selective oxidation), at the main oxide compound that generates Mn in matrix (plating starting material) surface.
Therefore, when the high mangaenese steel that will contain a large amount of Mn uses as the plating starting material, owing to before plating, form oxide on surface in the operation annealing process, so or the plating failure, even or coating also can take place man-hour and peel off adding in the plating success.
Up to now, in order to prevent above-mentioned galvanizing high manganese steel sheet plating failure, the prior art that had proposed already has following method: 1) as described in the patent documentation 5, add Sb, Sn, elements such as As, Te, prevent that alloying elements such as Mn, Si from forming oxide compound in surface diffusion, thereby carry out the method for plating; 2) as described in the patent documentation 6, add Si, form very thin Si oxide skin on the surface, thereby suppress the formation of Mn oxide, thereby carry out the method for plating; 3), before annealing, contain the Al material, thereby prevent the formation of Mn oxide, thereby carry out the method for plating by what vaccum gas phase sedimentation method (PVD) applied one deck 50nm to 1000nm as described in the patent documentation 7.
But, in above-mentioned existing method 1) in, can not be by in containing the high mangaenese steel of 5～35% manganese, adding Sb, the Sn of the trace below 0.05%, the surface oxidation that units such as As, Te usually prevent the manganese that oxidisability is very strong, therefore, have to add a large amount of above-mentioned high price alloying elements, cause expense to increase, therefore not ideal enough.
In above-mentioned existing method 2) in, therefore Si is stronger than the oxidisability of Mn, forms the oxide compound of stable film morphology, the problem that the wettability with fused zinc is difficult to improve occurs.
In addition, in above-mentioned existing method 3) in, must before the annealing of plating process, carry out the operation of vacuum vapor deposition, as oxidized easily by the Al of the plating material of vapour deposition, therefore, in annealing operation subsequently, the Al of vapour deposition in annealing atmosphere gas moisture and the effect of oxygen under form the aluminum oxide of wettability difference, therefore the plating problem of variation on the contrary appears.
As mentioned above, in the prior art, when the high mangaenese steel that will contain a large amount of manganese uses as the plating starting material,, be difficult to guarantee the good plating of hot-dip galvanized steel sheet and the good adhesive problem of plating so exist owing in annealing process, form thicker Mn oxide.
The prior art document:
Patent documentation:
Patent documentation 1:JP1992-259325
Patent documentation 2:WO93/013233
Patent documentation 3:WO99/001585
Patent documentation 4:WO02/101109
Patent documentation 5:KR 2007-0067593
Patent documentation 6:KR 2007-0067950
Patent documentation 7:KR 2007-0107138
Summary of the invention
The problem that invention will solve
The purpose of this invention is to provide a kind of with high mangaenese steel as the plating starting material, easily make the method for the high mangaenese steel hot-dip galvanized steel sheet of great coating surface qualities such as hot dipping plating and plating tackiness.
The means of dealing with problems
Below the present invention will be described.
The present invention relates to a kind of is the method that matrix is made the high mangaenese steel hot-dip galvanized steel sheet of great coating surface quality with high mangaenese steel, it is characterized in that, by adjusting dew point, Heating temperature and the heat-up time of atmosphere gas gas, in the mode that below next-door neighbour's matrix, forms subscale and porosity surface oxide compound high mangaenese steel is carried out selective oxidation, then in reduction atmosphere gas, reduce processing, carry out galvanizing then.
Preferably, the present invention relates to a kind of method of making the high mangaenese steel hot-dip galvanized steel sheet of great coating surface quality, it is characterized in that above-mentioned high mangaenese steel is composed as follows in weight %: C:0.1～1.5%, Mn:5～35%, Si:0.1～3wt%, Al:0.01～3%, Nb:0.03% are following, V:0.1% is following, S:0.01% is following, Fe and other unavoidable impurities of surplus; And, is that selective oxidation was carried out in the Heating temperature heating with 400～800 ℃ in 10～40 seconds in-20～-40 ℃ the reduction atmosphere gas with above-mentioned high mangaenese steel at dew point, form the subscale of manganese, form the oxide on surface of porous manganese on the surface, be with 800～850 ℃ temperature heating in-40～-60 ℃ the reduction atmosphere gas at dew point then, make oxide on surface reduction, be dipped in Al concentration then and be in the zinc-plated bath of 0.21～0.25wt% and carry out plating.
The invention effect
As mentioned above, according to the present invention, can be with the high mangaenese steel that contains 5～35% manganese that can't galvanizing with usual method as the plating starting material, make hot-dip galvanized steel sheet, in addition, also make the hot dip process steel plate as the plating starting material applicable to the general high-strength steel that will contain alloying elements such as Si, Mn, Al (for example, IF high-strength steel, two-phase complex tissue steel (DP), TRIP steel etc.).
Description of drawings
Fig. 1 is when being presented at 800 ℃ annealing temperature, the graphic representation that the thickness of oxide on surface (Mn oxide) changes with the variation of dew point.
The annealed material cross-section photograph of Fig. 2 formation degree of subscale when showing different dew point, (a) the expression dew point be-20 ℃ a situation, represents that (b) dew point is-40 ℃ a situation.
The photo of Fig. 3 variation of the surface shape of oxide on surface when showing different dew point, (a) the expression dew point is 0 ℃ a situation, and (b) the expression dew point be-20 ℃ a situation, and (c) the expression dew point is-40 ℃ a situation, represents that (d) dew point is-60 ℃ a situation.
Fig. 4 is for showing the process picture sheet of existing galvanizing (GI) operation and galvanizing of the present invention (GI) operation.
Embodiment
Below the present invention is described in detail.
The present invention is when with high mangaenese steel being matrix manufacturing high mangaenese steel hot-dip galvanized steel sheet, in the mode that below next-door neighbour's matrix, forms subscale and porosity surface oxide compound high mangaenese steel is carried out selective oxidation, then in reduction atmosphere gas, reduce processing, carry out galvanizing then, can produce the high mangaenese steel hot-dip galvanized steel sheet of great coating surface quality thus.
Dew point, Heating temperature and the heat-up time of the atmosphere gas gas when adjusting above-mentioned selective oxidation, form above-mentioned subscale and porosity surface oxide compound.
The inventor is in order to understand fully the occurrence cause of the high mangaenese steel plating failure that contains a large amount of manganese, the amount of increasing of material that the failure of high mangaenese steel plating takes place and oxide on surface is studied with the situation that the variation of the reductive condition of annealing atmosphere gas changes, the result as shown in Figure 1, variation along with the dew point of annealing atmosphere gas, the thickness of the Mn oxide that increase on the high mangaenese steel surface shows sizable difference, even change annealing conditions, because the formation of the thicker Mn oxide of film-type, plating performance also can't be guaranteed.
But, be in-40 ℃ the annealing atmosphere gas under the annealed situation at dew point, as shown in Figure 2, can find to have formed the subscale of manganese.
When forming subscale below next-door neighbour's matrix, this subscale has stoped the surface of the manganese of matrix to be increased, so the thickness attenuation of oxide on surface, and perhaps the shape of oxide on surface is not the continuous thin film shape, and shows alternate particle shape or netted.
But for high mangaenese steel, as shown in Figure 1, even can find that the thickness of oxide compound does not reduce yet, proportional on the contrary increase more than the critical dew point-40 that begins to form subscale ℃.
According to judge this be because high mangaenese steel and common carbon steel to compare manganese content very high, so even form the subscale of Mn oxide (MnO), a large amount of excessive manganese that exist also can increase on the surface, form oxide on surface.
But, when showing different dew point Fig. 3 of the shape of oxide on surface as can be known, when not forming-60 ℃ (Fig. 3 (d)) of subscale, formed very fine and close oxide on surface, and more than critical dew point-40 ℃ the time, oxide on surface demonstrates the shape that the oxide compound of particle shape tangles mutually, dew point is high more, and oxide particle is just thick more, and the gap between particle and the particle (pore, emptying aperture) is just big more.
That is to say, can know, when dew point is high, can form between the oxide particle oxide on surface that the existence owing to the gap interlinks.
Therefore, the inventor studies the subscale of below that can use next-door neighbour's matrix and the scheme of porosity surface oxide compound, results verification, when heating than the higher dew point of critical dew point that begins to form subscale, the selected oxidation of alloying elements such as manganese, formation contains the porosity surface oxide compound of more emptying aperture, when in strong reducing property atmosphere gas, it being carried out successive thermal treatment, the emptying aperture of oxide on surface plays the effect of the diffusion path (diffusion path) that is used for reductive atmosphere gas gas, thereby easily oxide on surface is reduced.
An example of the preferred high mangaenese steel that is suitable for can exemplify the high mangaenese steel that % meter by weight has following composition among the present invention: C:0.1～1.5%, Mn:5～35%, Si:0.1～3wt%, Al:0.01～3%, Nb:0.03% is following, V:0.1% is following, S:0.01% is following, Fe and other unavoidable impurities of surplus, and this high mangaenese steel is well known in the art.
Therefore, as an example, as shown in Figure 4, is that selective oxidation was carried out in the Heating temperature heating with 400～800 ℃ in 10～40 seconds in-20～-40 ℃ the reduction atmosphere gas with above-mentioned known high mangaenese steel at dew point, in matrix, to form the subscale of manganese, form the oxide on surface of the porous manganese of easy reductive on the surface, be with 800～850 ℃ temperature heating in-40～-60 ℃ the reduction atmosphere gas at dew point continuously then, make the oxide on surface reduction, guarantee material character, immerse Al concentration then and be in the zinc-plated bath of 0.21～0.25wt% and carry out plating, can not produce thus can the plating failure, the hot-dip galvanized steel sheet of the high mangaenese steel that the plating tackiness is good.
As mentioned above, in order to form the porosity surface oxide compound, in the selective oxidation operation, dew point is limited to-20～-40 ℃ by the subscale that forms matrix.
Above-mentioned dew point is during less than-40 ℃, because below critical dew point, so internal oxidation does not take place, and form fine and close oxide on surface, when dew point surpasses-40 ℃, form subscale, also form the porosity surface oxide compound, but when surpassing-20 ℃, owing to form very thick oxide on surface, so in the limited reduction treatment time, be difficult to make oxide on surface to reduce fully.
The Heating temperature of above-mentioned selective oxidation operation is limited at 400～800 ℃.
When above-mentioned Heating temperature during less than 400 ℃, can not successfully form subscale, when handling, reduction takes place once more that increase on the surface and oxidation from the manganese in the matrix, be difficult to guarantee the wettability of fused zinc; When surpassing 800 ℃,, in the limited reduction treatment time, be difficult to reduction, so be non-preferred version owing to form thicker oxide on surface.
Be limited to the heat-up time of above-mentioned selective oxidation operation 10～40 seconds.
When the heat-up time of the less than in the time of 10 seconds that is used for above-mentioned selective oxidation, even also can't be completed into internal oxidation under higher Heating temperature, the manganese of matrix takes place once more that increase on the surface and oxidation when reduction is handled, and wettability reduces; When surpass 40 seconds heat-up time, because excessive internal oxidation and formation oxide on surface need carry out the reduction of long period, so be non-preferred version.
In addition, as mentioned above, in order to make the porosity surface oxide compound reduction that selective oxidation forms and to guarantee material character, after selective oxidation, continuously dew point be in-40～-60 ℃ the reduction atmosphere gas with 800～850 ℃ temperature heating, oxide on surface is reduced fully.
For the porosity surface oxide compound reduction that selective oxidation is formed, the reason that the dew point of reduction atmosphere gas is limited to-40～-60 ℃ is as described below.
When the dew point of reduction atmosphere gas surpassed-40 ℃, the moisture in the reduction atmosphere gas and the ratio of oxygen were higher, are difficult to make Mn oxide to reduce fully; When dew point during less than-60 ℃, the manganese in the matrix increases and oxidation once more, is difficult to make oxide on surface to reduce fully.
Above-mentioned reduction temperature is high more, and reduction is just easy more, so be preferred version; But when surpassing 850 ℃, the problem that high temperature causes the strength degradation of steel can appear; During less than 800 ℃, make the required time of oxide on surface reduction longer, so preferably reduction temperature is defined as 800～850 ℃.
As mentioned above, the high mangaenese steel that will carry out selective oxidation and reduction processing is dipped in the zinc-plated bath that Al concentration is 0.21～0.25wt% and carries out plating, makes the high mangaenese steel hot-dip galvanized steel sheet.
The Al concentration that above-mentioned plating is bathed can suitably be 0.23～0.25wt%.
When being dipped in the plating bath through the reductive steel plate, preferential and the surface of steel plate reaction of Al during plating is bathed, form the Fe-Al-Zn layer of ductility, play the effect of the growth of the Zn-Fe intermetallic compound that suppresses fragile, so it is favourable that the Al concentration that plating is bathed maintains higher level, but bathe Al concentration above 0.25% the time, generate the floating scum silica frost of Fe-Al easily when plating, flow into coating layer and can cause macroscopic irregularity, so its upper limit is defined as 0.25%.
By the following examples the present invention is done more specific description.
(embodiment)
As shown in table 1 below, with thickness is 1.2mm, contain C:0.6 weight %, Mn:18 weight %, Si:0.2 weight %, Al:1.5 weight %, Nb:0.03 weight %, V:0.1 weight %, S:0.008 weight %, the Fe of surplus and the high mangaenese steel of other impurity, hydrogeneous 15%, surplus is a nitrogen, dew point is in 0 ℃～-60 ℃ the reduction atmosphere gas, kept 10～40 seconds with 400 ℃～800 ℃ annealing temperature, carry out the internal oxidation of manganese and the selective oxidation of surface oxidation, the oxide on surface that forms in the process with selective oxidation continuously is-20～-75 ℃ at atmosphere gas gas dew point, Heating temperature is under 800～850 ℃ the reduction treatment condition, carrying out reduction in 40 seconds handles, be cooled to 460 ℃ with 15 ℃/second speed of cooling then, being dipped in then and bathing temperature is 460 ℃, the Al concentration that plating is bathed is to carry out hot dip process during the galvanizing of 0.23wt% is bathed, and uses air knife (air knife) adjustment to make every plating adhesion amount be 60g/m
2, evaluation coating surface quality, that is, Mn surface degree of increasing, plating failure degree and plating tackiness the results are shown in the following table 1.
For the sample No.1,12 in the following table 1,17 and 27, do not evaluate Mn surface degree of increasing.
Above-mentioned manganese surface degree of increasing carries out the composition analysis of depth direction with glow discharge spectrometry (GDS), and the surface of manganese is increased degree and carried out quantitative evaluation with the height of peak value (peak) and length (highly * degree of depth).
As for above-mentioned plating failure degree, the appearance behind the galvanizing is taken pictures handle and obtain the area of plating failure part after, with following benchmark rating.
-1 etc.: the defective that does not have the plating failure
-2 etc.: the mean diameter of plating failure place is less than 1mm
-3 etc.: the mean diameter of plating failure place is 1～2mm
-4 etc.: the mean diameter of plating failure place is 2～3mm
-5 etc.: the mean diameter of plating failure place is more than the 3mm
In addition,, after having carried out the 0T-crooked test, adhesive tape test (taping test) is carried out in the outside portion of bending, the occurrence degree that coating is peeled off is estimated with following benchmark as for the plating tackiness of hot-dip galvanized steel sheet.
-1 etc.: do not have and peel off
-2 etc.: peel off less than 5%
-3 etc.: peel off 5～10%
-4 etc.: peel off 10～30%
-5 etc.: peel off more than 30%
Table 1:
As above shown in the table 1, under the selective oxidation condition that the present invention proposes, promptly in dew point is-20～-40 ℃ reduction atmosphere gas, with 40～-00 ℃ Heating temperature heating 10～40 seconds, form oxide on surface, be with 800～850 ℃ Heating temperature heating in-40～-60 ℃ the reduction atmosphere gas at dew point continuously, make the oxide on surface reduction, (sample No.4～5 in this case, 9～10,14～15,19～20,22～37,39～40,42～43), in matrix, form the subscale of manganese, form the oxide on surface of the porous manganese of easy reductive on the surface, when handling, reduction is reduced easily, the formation of subscale can prevent to increase once more and reoxidation from the manganese in the matrix, so can the plating failure can produce hot dip process the time, add the high manganese hot-dip galvanized steel sheet that the great coating surface quality that coating peels off does not take place man-hour.
On the other hand, under the situation of only carrying out anneal (sample No.1) though or carry out the reduction of selective oxidation processing and successive and handle, but the dew point during selective oxidation is (sample No.2～3 under the situation beyond the present invention, 6～8,11～13,16～18,21), internal oxidation does not take place below next-door neighbour's matrix, only form fine and close film-type oxide on surface, even perhaps forming the porosity surface oxide compound also forms very thickly, so the plating failure takes place, even plating success, unreduced oxide on surface also can cause coating to be peeled off adding man-hour on the interface, so be non-preferred version.
In addition, when the dew point of reductive condition and reduction temperature beyond the scope of the invention when (sample No.38,41,44), owing in atmosphere gas, have excessive moisture and oxygen, so the film-type oxide on surface that forms in the selective oxidation operation is difficult to reduce fully, so the plating failure can take place, perhaps coating takes place man-hour peel off adding, so be non-preferred version.
Claims (3)
1. one kind is the method that matrix is made the high mangaenese steel hot-dip galvanized steel sheet of great coating surface quality with high mangaenese steel,
It is characterized in that, by adjusting dew point, Heating temperature and the heat-up time of atmosphere gas gas, in the mode that below next-door neighbour's matrix, forms subscale and porosity surface oxide compound high mangaenese steel is carried out selective oxidation, then in reduction atmosphere gas, reduce processing, carry out galvanizing then.
2. the method for the high mangaenese steel hot-dip galvanized steel sheet of manufacturing great coating surface quality according to claim 1, it is characterized in that above-mentioned high mangaenese steel is composed as follows in weight %: C:0.1～1.5%, Mn:5～35%, Si:0.1～3wt%, Al:0.01～3%, Nb:0.03% are following, V:0.1% is following, S:0.01% is following, Fe and other unavoidable impurities of surplus; And, is that selective oxidation was carried out in the Heating temperature heating with 400～800 ℃ in 10～40 seconds in-20～-40 ℃ the reduction atmosphere gas with above-mentioned high mangaenese steel at dew point, form the subscale of manganese, form the oxide on surface of porous manganese on the surface, be with 800～850 ℃ temperature heating in-40～-60 ℃ the reduction atmosphere gas at dew point then, make oxide on surface reduction, be dipped in Al concentration then and be in the zinc-plated bath of 0.21～0.25wt% and carry out plating.
3. the method for the high mangaenese steel hot-dip galvanized steel sheet of manufacturing great coating surface quality according to claim 2 is characterized in that, the Al concentration of above-mentioned zinc-plated bath is 0.23～0.25wt%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020080132593A KR101079472B1 (en) | 2008-12-23 | 2008-12-23 | Method for Manufacturing High Manganese Hot Dip Galvanizing Steel Sheet with Superior Surface Property |
| KR10-2008-0132593 | 2008-12-23 |
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| CN101760712A true CN101760712A (en) | 2010-06-30 |
| CN101760712B CN101760712B (en) | 2012-08-22 |
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| CN2009102543783A Expired - Fee Related CN101760712B (en) | 2008-12-23 | 2009-12-22 | Production method for hot dip galvanized steel sheet in high manganese steel with great coating surface quality |
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| JP (1) | JP4990345B2 (en) |
| KR (1) | KR101079472B1 (en) |
| CN (1) | CN101760712B (en) |
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Also Published As
| Publication number | Publication date |
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| JP2010150660A (en) | 2010-07-08 |
| CN101760712B (en) | 2012-08-22 |
| KR101079472B1 (en) | 2011-11-03 |
| KR20100073819A (en) | 2010-07-01 |
| JP4990345B2 (en) | 2012-08-01 |
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